Catalyst component for polymerization of olefins

ABSTRACT

A catalyst component for polymerization of olefins which is prepared by reacting a magnesium alkoxide with a silicon compound having at least one hydrogen-silicon bond, contacting the reaction product with a carboxylic acid halide and/or carboxylic acid anhydride, and contacting the resulting contact product with a titanium compound.

This is a division, of application Ser. No. 642,462, filed 8/20/84 andnow U.S. Pat. No. 4,652,541.

DESCRIPTION OF THE INVENTION

1. Field of Technology

The present invention relates to a catalyst component for polymerizationof olefins. More particularly, the invention relates to (a) a catalystcomponent which provides olefin polymers having a high stereoregularityand a high bulk density in high yields, (b) an olefin polymerizationcatalyst system comprising the titanium halide containing catalystcomponent and an organo metal cocatalyst, and (c) the process forpolymerizing olefins in the presence of the catalyst system.

2. Background Technology

Heretofore, it has been known that a contact product of a halogen-freemagnesium compound and a titanium compound is useful as a catalystcomponent for the polymerization of olefins. It is, however, low incatalytic performance, and attempts have been made for improvement. Suchattempts include a process in which Mg(OR)₂ is contacted with titaniumtetrahalide in the presence of a halogenated silane represented bySiX_(p) R_(4-p) (X=halogen, R=hydrocarbyl radical) or in the presence ofsaid halogenated silane and an electron donor compound (Japanese PatentLaid-open No. 98076/1977), a process in which a magnesium compoundhaving the Mg-O-R linkage is contacted with a halogenating agent such asa silicon compound represented by the formula X_(m) SiR_(n) (X and Rbeing as defined above) in the presence of an electron donor compound(Japanese Patent Laid-open No. 43094/1978), a process in which the solidreaction product of a halogenated aluminum, an organic compound havingthe Si-O bond, and magnesium alcoholate is contacted with a tetravalenttitanium compound having at least one halogen atom (U.S. Pat. No.4,242,479), a process in which the reaction product of a magnesiumcompound, titanium compound, and silicon compound is contacted with atleast one kind of halogenated aluminum compound (Japanese PatentLaid-open No. 155205/1981).

The catalyst components obtained according to the above-mentionedprocesses, however, are poor in catalytic activity and stereoregularityand provide polymers having a low bulk density. In addition to theabove-mentioned catalyst components, there is known one which isobtained by contacting a magnesium compound, an electron donor compound,a silicon compound having the Si-H bond, and a titanium halide compoundall together (Japanese Patent Laid-open No. 92009/1982). According tothis process, the magnesium compound is essentially a magnesium halideand the silicon compound and titanium halide are used simultaneously forcontacting. Therefore, the resulting product is not necessarilysatisfactory.

SUMMARY OF THE INVENTION

In order to produce from a halogen-free magnesium compound a catalystcomponent which can be made into a catalyst which exhibits highstereoregularity and high catalytic activity and provides olefinpolymers having a high bulk density, the present inventors carried outextensive researches, which led to the findings that the object can beachieved with a solid substance obtained by reacting a magnesiumhydrocarbyl oxide with a silicon compound having the hydrogen-siliconbond, contacting the reaction product with a carboxylic acid halideand/or carboxylic acid anhydride, and contacting the resulting contactproduct with a titanium compound. The present invention has beencompleted based on these findings.

The essence of this invention resides in a catalyst component forpolymerization of olefins which is prepared by reacting a magnesiumhydrocarbyl oxide with a silicon compound having the hydrogen-siliconbond, contacting the reaction product with a carboxylic acid halideand/or carboxylic acid anhydride, and contacting the resulting contactproduct with a titanium compound.

Raw Materials for Catalyst Component

The raw materials used for preparing the catalyst component of thisinvention are described below.

(A) Magnesium Hydrocarbyl Oxide

The magnesium hydrocarbyl oxide used in this invention is represented bythe formula Mg(OR)(OR'), wherein R and R' are alkyl, alkenyl,cycloalkyl, aryl, or aralkyl groups having 1 to 20 carbon atoms,preferably 1 to 10 carbon atoms, and R and R" may be the same ordifferent.

These compounds include, for example, Mg(OCH₃)₂, Mg(OC₂ H₅)₂ Mg(OCH₃)(OC₂ H₅), Mg(Oi-C₃ H₇)₂, Mg(OC₃ H₇)₂, Mg(OC₄ H₉)₂, Mg(Oi-C₄ H₉)₂, Mg(OC₄H₉)(O-iC₄ H₉), Mg(OC₄ H₉)(Osec-C₄ H₉), Mg(OC₆ H₁₃)₂, Mg(OC₈ H₁₇)₂,Mg(OC₆ H₁₁)₂, Mg(OC₆ H₅)₂, Mg(OC₆ H₄ CH₃)₂, and Mg(OCH₂ C₆ H₅)₂.

These magnesium hydrocarbyl oxides should preferably be dried beforeuse, and more preferably be dried with heating under reduced pressure.These magnesium hydrocarbyl oxides may be obtained commercially or maybe synthesized according to the known methods.

These magnesium hydrocarbyl oxides may be contacted with an inorganic ororganic inert solid substance prior to use.

Suitable inorganic solid substances include metal compounds in the formof sulfate, hydroxide, carbonate, phosphate, or silicate. Examples ofsuch compounds include Mg(OH)₂, BaCO₃, and Ca₃ (PO₄)₂.

Suitable organic solid substances include low-molecular aromatichydrocarbons such as durene, anthracene, napthalene, and diphenyl. Theyalso include high-molecular compounds such as polyethylene,polypropylene, polyvinyl toluene, polystyrene, polymethyl methacrylate,polyamide, polyester, and polyvinyl chloride.

(B) Silicon Compound The silicon compound used in this invention may beany compound having the hydrogen-silicon bond. It is represented by theformula H_(m) R_(n) SiX_(r), wherein R is (1) a hydrocarbon group, (2)R'O-(R' is a hydrocarbon group), (3) R² R³ N--(R² and R³ are hydrocarbongroups), or (4) R⁴ COO- (R⁴ is a hydrogen atom or hydrocarbon group); Xis a halogen atom; and m is 1 to 3, 0≦r<4, and m+n+r=4. When n isgreater than 1, R may be the same or different.

The hydrocarbon groups represented by R, R¹, R², R³, and R⁴ includealkyl, alkenyl, cycloalkyl, aryl, and aralkyl groups of carbon number 1to 16. The alkyl group includes, for example, methyl, ethyl, propyl,n-butyl, isobutyl, n-hexyl, n-octyl, 2-ethylhexyl, and n-decyl. Thealkenyl group includes, for example, vinyl, allyl, isopropenyl,propenyl, and butenyl. The cycloalkyl group includes, for example,cyclopentyl and cyclohexyl. The aryl group includes, for example,phenyl, tolyl, and xylyl. The aralkyl group includes, for example,benzyl, phenetyl, and phenylpropyl.

Preferable among them are lower alkyl groups such as methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, and t-butyl, and aryl groups suchas phenyl and tolyl.

X denotes halogen atoms such as chlorine, bromine, and iodine. Thepreferred halogen is chlorine.

The silicon compounds are exemplified by HSiCl₃, H₂ SiCl₂, H₃ SiCl, HCH₃SiCl₂, HC₂ H₅ SiCl₂, H(t-C₄ H₉)SiCl₂, HC₆ H₅ SiCl₂, H(CH₃)₂ SiCl, H(i-C₃H₇)₂ SiCl, H₂ C₂ H₅ SiCl, H₂ (n-C₄ H₉)SiCl, H₂ (C₆ H₄ CH₃)SiCl,HSi(CH₃)₃, HSiCH₃ (OCH₃)₂, HSiCH₃ (OC₂ H₅)₂, HSi(OCH₃)₃, (C₂ H₅)₂ SiH₂,HSi(CH₃)₂ (OC₂ H₅), HSi(CH₃)₂ [N(CH₃)₂ ], HSiCH₃ (C₂ H₅)₂, HSiC₂ H₅ (OC₂H₅)₂, HSiCH₃ [N(CH₃)₂ ]₂, C₆ H₅ SiH₃, HSi(C₂ H₅)₃, HSi(OC₂ H₅)₃,HSi(CH₃)₂ [N(C₂ H₅)₂ ], C.sub. 6 H₅ CH₃ SiH₂, C₆ H₅ (CH₃)₂ SiH, (n-C₃H₇)₃ SiH, HSiCl(C₆ H₅)₂, H₂ Si(C₆ H₅)₂, HSi(C₆ H₅)₂ CH₃, (n-C₅ H₁₁ O)₃SiH, HSi(C₆ H₅)₃, and (n-C₅ H₁₁) ₃ SiH. Another example of the compoundsnot covered by the above formula include (ClCH₂ CH₂ O)₂ -CH₃ SiH,Hsi(OCH₂ CH₂ Cl)₃, [H(CH₃)₂ Si]₂ O, [H(CH₃)₂ Si]₂ NH, (CH₃)₃ SiOSi(CH₃)₂H, [H(CH₃)₂ Si]₂ C₆ H₄ [H(CH₃)₂ SiO]₂ -Si(CH₃)₂, [(CH 3)₃ SiO]₂ SiHCH₃,[(CH₃)₃ SiO]₃ SiH, and ##STR1##

Preferable among these halogenated silicon compounds are those which arerepresented by the formula in which R is a hydrocarbon, n is 0 to 2, andr is 1 to 3. They are HSiCl₃, H₂ SiCl₂, H₃ SiCl, HCH₃ SiCl₂, HC₂,H₅SiCl₂, H(t-C₄ H₉)SiCl₂, HC₆ H₅ SiCl₂, H(CH₃₂ SiCl, H(i-C₃ H₇)₂ SiCl, H₂C₂ H₅ SiCl, H₂ (n-C₄ H₉)SiCl, H₂ (C₆ H₄ CH₃)SiCl, and HSiCl- (C₆ H₅)₂.Most preferable among them are HSiCl₃, HCH₃ SiCl₂, and H(CH₃)₂ SiCl.Especially preferred among the silicon compounds is HSiCl₃.

(C) Carboxylic Acid Halide and Carboxylic Acid Anhydride

Examples of the carboxylic anhydride include aliphatic monocarboxylicanhydrides such as acetic anhydride, propionic anhydride, butyricanhydride, valeric anhydride, and caproic anhydride; aliphaticolefinmonocarboxylic anhydrides such as acrylic anhydride, crotonicanhydride, and methacrylic anhydride; alicyclic carboxylic anhydridessuch as cyclohexanemonocarboxylic anhydride, cyclohexenemonocarboxylicanhydride, cis-1, 2-cyclohexanedicarboxylic anhydride, andcis-4-cyclohexene-1, 2-dicarboxylic anhydride; aromatic monocarboxylicanhydrides such as benzoic anhydride, p-toluylic anhydride,p-ethylbenzoic anhydride, and p-methoxybenzoic anhydride; and aromaticdicarboxylic anhydrides such as phthalic anhydride. Preferable amongthem are aromatic carboxylic anhydrides, and especially benzoicanhydride.

Examples of the carboxylic acid halides includes aliphaticmonocarboxylic acid halides such as acetyl chloride, propionyl chloride,and n-butylyl chloride; and acid bromides such as acetyl bromide andn-butylyl bromide; and acid iodides such as acetyl iodide and n-butylyliodide, aliphatic monoolefincarboxylic acid halides such as acrylchloride, crotonyl chloride, and methacryl chloride; acid bromides suchas acryl bromide and methacryl bromide; and acid iodides such as acryliodide and methacryl iodide, alicyclic carboxylic acid halides such ascyclohexanecarboxylic acid chloride, cis-4-methylcyclohexanecarboxylicacid chloride, 1-cyclohexenecarboxylic acid chloride,cyclohexanecarboxylic acid bromide, and cis-4-methylhexenecarboxylicacid bromide, aromatic monocarboxylic acid halides such as benzoylchloride, p-toluic acid chloride, p-ethylbenzoic acid chloride, andp-methoxybenzoic acid chloride; acid bromides such as benzoyl bromide;and acid iodides such as benzoyl iodide, and aromatic dicarboxylic acidhalides such as phthalic acid dichloride. Preferable among them arearomatic carboxylic acid halides and especially benzoyl chloride.

(D) Titanium Compound

The titanium compound used in this invention includes divalent,trivalent, and tetravalent titanium compounds. They are exemplified bytitanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium,trichlorobutoxytitanium, dichlorodibutoxytitanium,dichlorodiethoxytitanium, dichlorodiphenoxytitanium,chlorotiethoxytitanium, chlorotributoxytitaniumn, tetrabotoxytitanium,and titanium trichloride. Preferable among them are tetravalent titaniumhalides such as titanium tetrachloride, trichloroethoxytitanium,dichlorodibutoxytitanium, and dichlorodiphenoxytitanium, and mostpreferable is titanium tetrachloride.

Preparation of Catalyst Component

The catalyst component of this invention is prepared by reacting amagnesium hydrocarbyl oxide (component A) with the silicon compoundcontaining at least one H-Si bond (component B), contacting the reactionproduct with a carboxylic acid halide and/or carboxylic acid anhydride(component C) (referred to as carboxylic acid derivatives), andcontacting the resulting contact product with a titanium compound(component D). The process is described below.

(1) Reaction of Magnesium Alkoxide with Silicon Compound

The reaction of a magnesium hydrocarbyl oxide (component A) with thesilicon compound containing at least one H-Si bond (component B) isaccomplished by contacting the two components with each other. Thecontacting can be accomplished by mixing/stirring or mechanicallycopulverizing the two compounds in the presence or absence of ahydrocarbon. Preferably, the two components should be mixed and stirredin a hydrocarbon.

The Preferred hydrocarbon is a saturated aliphatic, saturated alicyclic,or aromatic hydrocarbon of carbon number 6 to 12 such as hexane,heptane, octane, cyclohexane, benzene, toluene, and xylene.

One mol of component A is contacted with 0.5 to 10 mol, preferably 1 to5 mol of component B. Usually, the contacting is performed at 0° to 200°C. for 0.5 to 100 hours. More than one kind each of component A andcomponent B may be used.

The hydrocarbon may be used in any amount; but it should preferably beless than 100 ml for 1 g of component A.

In the case where a halogenated silicon compound is used as component B,a gas is formed when component A is contacted with component B. Thisindicates that the reaction is taking place. The quantity of siliconatom in the reaction product, which is insoluble in an inert solvent,particularly n-hexane or n-heptane, at 65° C., is more than 8 wt%.

The contact product of component A and component B is separated from thereaction system, and is used for the subsequent contacting. Ifnecessary, it may be washed with an inert hydrocarbon such as one whichis used in the contacting of component A and component B, prior to thesubsequent contacting. This washing may be carried out with heating.

(2) Contacting with Carboxylic Acid Derivative

The contacting of the reaction product obtained in the above step (1)with a carboxylic acid derivative (component C) may be accomplished bymixing and stirring them together in the presence or absence of an inerthydrocarbon, or by mechanically copulverizing them. The inerthydrocarbon includes hexane, heptane, octane, cyclohexane, benzene,toluene, and xylene.

The contacting by mechanical copulverization should be carried out at 0°to 100° C. for 0.1 to 100 hours. The contacting by mere stirring shouldbe carried out at 0° to 150° C. for 0.5 to 10 hours.

Component C is used in an amount of 0.01 to 10 gram mol, particularly0.05 to 1 gram mol, for 1 gram atom of magnesium in the reaction productof magnesium alkoxide and silicon compound.

(3) Contacting with Titanium Compound

The contact product obtained in the above step (2) is then contactedwith a titanium compound (component D). Prior to contacting withcomponent D, the contact product may be washed with a proper cleaningagent such as the above-mentioned hydrocarbon.

The two components may be contacted with each other as such; but it ispreferable that they are mixed and stirred in a hydrocarbon. Thehydrocarbon includes hexane, heptane, octane, cyclohexane, benzene,toluene, and xylene.

Component D is used in an amount more than 0.1 gram mol, particularly 1to 50 gram mol, for 1 gram atom of magnesium in the contact product.

The contacting should be carried out at 0° to 200° C. for 0.5 to 20hours, and preferably at 60° to 150° C. for 1 to 5 hours.

The contacting with component D should preferably be carried more thanonce. Where the previous contacting has been carried out in ahydrocarbon, the contact product should be separated from thehydrocarbon prior to the subsequent contacting.

The solid substance obtain as mentioned above is washed, if required,with an inert hydrocarbon such as hexane, heptane, octane, cyclohexane,benzene, toluene, and xylene, followed by drying, whereby there isobtained the catalyst component of this invention.

The catalyst component of this invention is powder having a specificsurface area of 50 to 650 m² /g as measured by BET method at theadsorption temperature of liquid nitrogen, a pore volume of 0.05 to 0.40cc/g, and a narrow particle size distribution.

Catalyst for Polymerization of Olefin

The titanium-containing solid catalyst component of this invention iscombined with an organoaluminum compound to provide a catalyst forhomopolymerization of an olefin or for copolymerization of an olefin andother olefin.

Organoaluminum Compound

The organoaluminum compound to be combined with the catalyst componentis one which is represented by the formula R_(n) AlX_(3-n), wherein R isan alkyl group or aryl group, X is a halogen atom, alkoxy group, orhydrogen atom, n is an arbitrary number in the range of 1≦n<3. Preferredones are alkyl aluminum compounds and a mixture thereof or complexthereof having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms,such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkylaluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminummonoalkoxide, and dialkyl aluminum monohydride. Examples of suchcompounds include trialkyl aluminum such as trimethyl aluminum, triethylaluminum, tripropyl aluminum, triisobutyl aluminum, and trihexylaluminum; dialkyl aluminum monohalide such as dimethyl aluminumchloride, diethyl aluminum chloride, diethyl aluminum bromide, diethylaluminum iodide, and diisobutyl aluminum chloride; monoalkyl aluminumdihalide such as methyl aluminum dichloride, ethyl aluminum dichloride,methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminumdiiodide, and isobutyl aluminum dichloride; alkyl aluminum sesquihalidesuch as ethyl aluminum sesquichloride; dialkyl aluminum monoalkoxidesuch as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethylaluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminumethoxide, and diisobutyl aluminum phenoxide; and dialkyl aluminumhydride such as dimethyl aluminum hydride, diethyl aluminum hydride,dipropyl aluminum hydride, and diisobutyl aluminum hydride.

Preferable among them is trialkyl aluminum, particularly triethylaluminum and triisobutyl aluminum. The trialkyl aluminum can be used incombination with the other organoaluminum compound such as commerciallyavailable diethyl aluminum chloride, ethyl aluminum dichloride, ethylaluminum sesquichloride, diethyl aluminum ethoxide, and diethyl aluminumhydride, and a mixture or complex thereof.

In addition, the organoaluminum compound may be used alone or incombination with an electron donor compound. Preferable ones arecarboxylic acids, carboxylic esters, alcohols, ethers, ketones, amines,amides nitriles, aldehydes, alcoholates, phosphoamides, thioethers,thioesters, and carbonic esters, and phosphorus, arsenic, and antimonycompounds in which these atoms are bonded to an organic group through acarbon or oxygen. Preferable among them are carboxylic esters, alcohols,and ethers.

Examples of carboxylic esters include butyl formate, ethyl acetate,butyl acetate, ethyl acrylate, ethyl butyrate, isobutyl isobutyrate,methyl methacrylate, diethyl maleate, diethyl tartrate, ethylcyclohexanecarbonate, ethyl benzoate, ethyl p-methoxybenzoate, methylp-methylbenzoate, ethyl p-tert-butylbenzoate, dibutyl phthalate, diallylphthalate, and ethyl alpha-naphthoate. They are not limitative.Preferable among them are alkyl esters of aromatic carboxylic acid,particularly C₁₋₈ alkyl esters of benzoic acid or nucleus-substitutedbenzoic acid such as p-methylbenzoic acid and p-methoxy benzoic acid.

The alcohols are represented by the formula ROH, wherein R is an alkyl,alkenyl, cycloalkyl, aryl, or aralkyl group of carbon number 1 to 12.Examples of the alcohols include methanol, ethanol, propanol,isopropanol, butanol, isobutanol, pentanol, hexanol, octanol,2-ethylhexanol, cyclohexanol, benzyl alcohol, and allyl alcohol.

The ethers are represented by the formula ROR', wherein R and R' arealkyl, alkenyl, cycloalkyl, aryl, or aralkyl groups of carbon number 1to 12, and R and R' may be the same or different. Examples of the ethersinclude diethyl ether, diisopropyl ether, dibutyl ether, diisobutylether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethylallyl ether, butyl allyl ether, diphenyl ether, anisole, and ethylphenyl ether.

The electron donor compound may be used when an organoaluminum compoundis used in combination with the catalyst component, or may be used afterbeing contacted with an organoaluminum beforehand.

The organoaluminum compound is used in an amount of 1 to 2000 gram mol,preferably 20 to 500 gram mol, for 1 gram atom of titanium in thecatalyst component.

The ratio of the organoaluminum compound to the electron donor compoundis such that aluminum in the organoaluminum compound is 0.1 to 40 gramatom, preferably 1 to 25 gram atom, for 1 mol of the electron donorcompound.

Polymerization of Olefin

The catalyst composed of the catalyst component prepared as mentionedabove and an organoaluminum compound (and an electron donor compound) isuseful as a catalyst for homopolymerization of monoolefin orcopolymerization of monoolefin and other monoolefin or diolefin. Itexhibits outstanding performance as a catalyst for homopolymerization ofan alpha-olefin of carbon number 3 to 6, such as propylene, 1-butene,4-methyl-1-pentene, and 1-hexene, or random or block copolymerization ofthe above-mentioned alpha-olefins with one another or with ethylene; andfor homopolymerization of ethylene or random or block copolymerizationof ethylene with an alpha-olefin of carbon number 3 to 10, such aspropylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene.

The polymerization may be performed either in gas phase or liquid phase.The liquid phase polymerization may be accomplished in an inerthydrocarbon such as n-butane, isobutane, n-pentane, isopentane, hexane,heptane, octane, cyclohexane, benzene, toluene, and xylene, or in theliquid monomer. The polymerization temperature is usually -80° C. to+150° C., preferably 40° C. to 120° C. The polymerization pressure is 1to 60 atm. The molecular weight modification of the resulting polymer isaccomplished in the presence of hydrogen or other known molecular weightmodifiers. In the copolymerization of olefin, the quantity of otherolefin to be copolymerized is usually less than 30 wt%, particularly 0.5to 15 wt%, based on the olefin. The polymerization with the catalystsystem of this invention may be performed continuously or batchwiseunder the commonly used conditions. The copolymerization may beaccomplished in one step or in two or more steps.

EFFECT OF INVENTION

The catalyst component of this invention is useful for the production ofpolyolefins, particularly isotactic polypropylene, ethylene-propylenerandom copolymer, and ethylene-propylene block copolymer.

The polymerization catalyst made from the catalyst component of thisinvention exhibits a high catalytic activity and stereoregularities andkeeps it high activity for a long time. It provides polymer powderhaving a high bulk density and flowability.

EXAMPLES

The invention is described in more detail with reference to thefollowing examples and application examples. The scope of this inventionis not limited by these examples. Percent (%) in the examples andapplication examples means wt%, unless otherwise indicated.

The specific surface area (S.A.) and pore volume (P.V.) of the catalystcomponent were measured by using SORPTOMATIC, Model 1810, made by CARLOERBA.

The catalytic activity Kc is the quantity (g) of polymer formed per 1 gof catalyst, and Kt is the quantity (kg) of polymer formed per 1 g oftitanium in the catalyst.

The heptane insoluble (referred to as HI hereinafter) which indicatesthe ratio of crystalline fractions in the polymer is the quantity ofresidues which remain after extraction for 6 hours with boilingn-heptane in a Soxhlet apparatus of improved type.

The melt flow rate (MFR) and melt index (MI) were measured according toASTM-D1238. The bulk density was measured according to ASTM-D1895-69,Method A.

EXAMPLE 1 Contacting of Magnesium Diethoxide with Trichlorosilane

Into a 2-liter glass reactor equipped with a reflux condenser, droppingfunnel, and stirrer and replaced with nitrogen were charged 120 g (1.05mol) of commercial magnesium diethoxide and 680 ml of n-heptane. Withstirring at room temperature, a mixture of 356 g (2.63 mol) oftrichlorosilane and 250 ml of n-heptane was added dropwise from thedropping funnel over 45 minutes. Stirring was continued for 6 hours at70° C. During the reaction, a gas composed mainly of ethylene and ethylchloride formed. The resulting solids were filtered off at 70° C. andthen washed by stirring in 600 ml of n-hexane at 65° C. for 10 minutes.The supernatant liquid was removed by decantation. Washing with n-hexanewas repeated 4 times, and the solids were dried at 60° C. for 1 hourunder reduced pressure. Thus there was obtained 164 g of solid component(1). This solid component was found to contain 13.0% of magnesium, 13.8%of silicon, and 47.8% of chlorine, and to have a specific surface areaof 31 m² /g and a pore volume of 0.08 cc/g.

Contacting with Benzoyl Chloride

18 g of the solid component (I) was placed in a 300-ml stainless steel(SUS316) mill pot containing 100 pieces of stainless steel (SUS316)balls, 12 mm in diameter, under the nitrogen atmosphere. Then 4.5 g ofbenzoyl chloride was added to the mill pot. The mill pot was mounted ona shaker and shaken for 1 hour for crushing. Thus there was obtained asolid component (II).

Contacting with Titanium Tetrachloride

7 g of the solid component (II) was placed in a 200-ml glass reactorequipped with a stirrer under the nitrogen atmosphere. Then 40 ml oftoluene and 60 ml of titanium tetrachloride were added, followed bystirring at 90° C. for 2 hours. The resulting solid substance wasfiltered off at 90° C. After washing 7 times with 90 ml portions ofn-hexane at room temperature, the solids were dried at room temperaturefor 1 hour under reduced pressure. Thus there was obtained 5.1 g ofcatalyst component containing 3.0% of titanium, 17.3% of magnesium,57.2% of chlorine, and 3.9% of silicon. The catalyst component was foundto have a specific surface area of 280 m² /g and a pore volume of 0.23cc/g.

EXAMPLE 2

A catalyst component was prepared in the same way as in Example 1,except that benzoyl chloride was replaced by benzoic anhydride. Table 1shows the composition of the resulting catalyst component.

EXAMPLE 3

7 g of the solid component (II) obtained in Example 1 was placed in a200-ml glass reactor equipped with a stirrer under the nitrogenatmosphere. Then 40 ml of toluene and 60 ml of titanium tetrachloridewere added, followed by stirring at 90° C. for 2 hours. The supernatantliquid was removed by decantation. After washing four times with 90 mlportions of toluene at 60° C., 40 ml of toluene and 60 ml of titaniumtetrachloride were added, followed by stirring at 90° C. for 2 hours.The resulting solid substance was filtered off at 90° C. After washing 7times with 90 ml portions of n-hexane at room temperature, the solidswere dried at room temperature for 1 hour under reduced pressure. Thusthere was obtained a catalyst component having the composition as shownin Table 1.

EXAMPLES 4 to 6

Solid component (II) was prepared in the same way as in Example 1,except that benzoyl chloride was replaced by p-toluylic acid chloride(Example 4), benzoic anhydride (Example 5), and phthalic anhydride(Example 6). The solid component (II) was contacted with titaniumtetrachloride twice in the same was as in Example 3 to give catalystcomponents. Table 1 shows the compositions of the resulting catalystcomponents.

EXAMPLE 7

Solid component (II) was prepared in the same way as in Example 1,except that trichlorosilane used for the contacting of magnesiumdiethoxide was replaced by methyldichlorosilane.

The solid component (II) was contacted with titanium tetrachloride twicein the same way as in Example 3 to give a catalyst component. Table 1shows the composition of the resulting catalyst component.

EXAMPLE 8

Solid component (II) was prepared in the same way as in Example 1,except that trichlorosilane was replaced by methyldichlorosilane andbenzoyl chloride was replaced by benzoic anhydride.

The solid component (II) was contacted with titanium tetrachloride twicein the same way as in Example 3 to give a catalyst component having thecomposition as shown in Table 1.

EXAMPLE 9

8.3 g of the solid component (I) obtained in Example 1 was placed in a200-ml glass reactor equipped with a stirrer under the nitrogenatmosphere. Then 80 ml of heptane was added to make slurry. Then, 3.7 gof benzoyl chloride was added, followed by reaction at 70° C. for 2hours. The resulting solid substance was filtered off at 70° C. andwashed five times with 90 ml portions of n-hexane at 60° C.

This solid substance was contacted with titanium tetrachloride in thesame way as in Example 3 to give a catalyst component having thecomposition as shown in Table 1.

EXAMPLE 10

A catalyst component was prepared in the same way as in Example 9,except that benzoyl chloride was replaced by benzoic anhydride. Table 1shows the composition of the resulting catalyst component.

COMPARATIVE EXAMPLE 1

Into the same mill pot as used in Example 1 were charged under thenitrogen atmosphere 31.5 g of commercial magnesium diethoxide and 10.0 gof benzoic anhydride. The mill pot was shaken on a shaker for 15 hours.

5.0 g of the resulting ground solid was placed in a 500-ml glasscontainer equipped with a stirrer, and 300 ml of n-heptane was added.Then 9 ml of titanium tetrachloride was added dropwise over 15 minutesat room temperature. Further, 35 ml of trichlorosilane was addeddropwise in the same way, followed by stirring at 90° C. for 2 hours.

The resulting solid substance was filtered off at 90° C. and washed 6times with 150 ml portions of n-hexane at room temperature. The solidsubstance was dried at room temperature for 1 hour under reducedpressure. Table 1 shows the compositions of the resulting catalystcomponent.

COMPARATIVE EXAMPLE 2

Comparative Example 1 was repeated, except that benzoic anhydride wasreplaced by 7.5 ml of ethyl benzoate. Table 1 shows the composition ofthe resulting catalyst component.

                  TABLE 1                                                         ______________________________________                                               Silicon Compound-                                                             treated Solid                                                                            Catalyst Component                                                 Composition (%)                                                                          Composition (%)                                                    Mg   Si     C1     Mg   Ti    Si    C1                                 ______________________________________                                        Example                                                                       1        13.0   13.8   47.8 17.3 3.0   3.9   57.2                             2        13.0   13.8   47.8 16.9 4.3   3.3   58.5                             3        13.0   13.8   47.8 17.8 4.1   2.9   56.9                             4        13.0   13.8   47.8 17.2 3.8   2.7   57.4                             5        13.0   13.8   47.8 16.8 3.7   2.9   57.1                             6        13.0   13.8   47.8 17.5 4.0   3.2   56.9                             7        12.8   14.2   48.3 17.1 4.2   3.2   58.5                             8        12.8   14.2   48.3 17.4 4.3   3.3   57.9                             9        13.0   13.8   47.8 16.8 3.8   2.5   58.3                             10       13.0   13.8   47.8 17.3 3.9   2.8   58.1                             Comparative                                                                   Example                                                                       1        --     --     --   15.2 5.3   0.6   44.1                             2        --     --     --   14.3 5.9   0.6   42.6                             ______________________________________                                    

APPLICATION EXAMPLE 1 Polymerization of Propylene

20.1 mg of catalyst component obtained in Example 1, 3.15 ml of triethylaluminum (abbreviated as TEAL hereinafter) solution in n-heptane, and0.17 ml of ethyl p-methoxybenzoate were mixed. After standing for 5minutes, the mixture was added to a 1.5-liter stainless steel (SUS 32)autoclave equipped with a stirrer under the nitrogen atmosphere. (Then-heptane solution of TEAL contains 1 mol of TEAL in 1 liter ofn-heptane, and 3.15 ml of the solution corresponds to 250 gram atom ofaluminum for 1 gram atom of titanium in the catalyst component. 0.17 mlof ethyl p-methoxybenzoate corresponds to 0.33 mol for 1 gram atom ofaluminum in TEAL.) Then, 0.6 liter of hydrogen as the molecular weightmodifier and 0.8 liter of liquefied propylene were forced into theautoclave. The reaction system was heated to 70° C., and thepolymerization of propylene was carried out for 1 hour. After thepolymerization was complete, unreacted propylene was purged. Thus therewas obtained 191.0 g of white polypropylene powder having an HI of 93.8%(heptane insolubles indicating the crystalline fraction in the polymer),an MFR of 4.2 (melt flow rate), and a bulk density of 0.36 g/cm³.

Kc=9,500 [quantity (g) of polymer formed per 1 g of catalyst]

Kt=317 [quantity (kg) of polymer formed per 1 g of Ti in the catalyst]

APPLICATION EXAMPLES 2 to 12

Polymerization of propylene was carried out in the same way as inApplication Example 1, except that the catalyst component obtained inExample 1 was replaced by those which were obtained in Examples 2 to 10and Comparative Examples 1 and 2. The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Applica-                            MFR   Bulk                                tion   Catalyst   Kc      Kt   HI   (g/10 density                             Example                                                                              Component  (g)     (kg) (%)  min)  (g/cm.sup.3)                        ______________________________________                                        1      Example 1   9,500  317  93.8 4.2   0.36                                2      Example 2   9,700  294  94.0 4.3   0.37                                3      Example 3  11,500  397  94.5 3.8   0.37                                4      Example 4  10,100  374  94.2 3.9   0.38                                5      Example 5  12,100  417  94.8 3.5   0.37                                6      Example 6   9,500  297  93.9 4.3   0.38                                7      Example 7  10,600  331  94.5 3.6   0.38                                8      Example 8  11,400  345  94.7 3.2   0.38                                9      Example 9  11,300  452  94.7 3.5   0.37                                10     Example 10 12,500  446  95.0 3.0   0.38                                11     Comparative                                                                                480    9   86.7 --    --                                         Example 1                                                              12     Comparative                                                                                600    10  85.1 --    --                                         Example 2                                                              ______________________________________                                    

What is claimed is:
 1. A process for the polymerization of olefins whichcomprises homopolymerizing ethylene or copolymerizing ethylene with analpha-olefin in the presence of a catalyst system comprising(a) atitanium containing catalyst component obtained by reacting (A)Mg(OR)(OR') with (B) a silicon compound having at least onesilicon-hydrogen bond, contacting the reaction product with (C) acarboxylic acid halide, a carboxylic acid anhydride, or mixturesthereof, and contacting the resulting contact product with a divalent,trivalent, or tetravalent titanium compound selected from titaninumhalides, alkoxy titanium compounds and haloalkoxy titanium compounds,wherein R and R' are radicals selected from alkyl, alkenyl, cycloalkyl,aryl, and aralkyl radicals and R and R' may be the same or different (b)and an organoaluminum cocatalyst.
 2. The process in accordance withclaim 1 wherein the titanium compound is tetravalent.
 3. The process inaccordance with claim 2 wherein the titanium compound is titaniumtetrachloride.
 4. The process in accordance with claim 1 wherein R andR' are alkyl radicals having from 1-8 carbon atoms, the silicon compoundis trichlorosilane, and the carboxylic acid derivative is selected frombenzoyl chloride and benzoic anhydride.
 5. The process of claim 4wherein R and R' are ethyl.
 6. The process in accordance with claim 1wherein the catalyst component is recovered and prior to washing,contacted at least an additional time with the titanium compound.